U.S. patent number 8,198,503 [Application Number 12/272,967] was granted by the patent office on 2012-06-12 for disposable absorbent articles comprising odor controlling materials.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Sharon Anne Keegan, Gregory Scot Miracle, Edward Joseph Urankar, Randall Alan Watson.
United States Patent |
8,198,503 |
Urankar , et al. |
June 12, 2012 |
Disposable absorbent articles comprising odor controlling
materials
Abstract
The present inventions relates to a disposable absorbent
articles, including diapers and sanitary napkins, comprising a
bleach activator system for controlling odors associated with
bodily fluids. The bleach activator system may comprise a peroxygen
bleach compound (including a source of hydrogen peroxide) and a
bleach activator compound capable of generating a peroxyacid
in-situ within the absorbent article.
Inventors: |
Urankar; Edward Joseph (Mason,
OH), Keegan; Sharon Anne (Lawrenceburg, IN), Watson;
Randall Alan (Loveland, OH), Miracle; Gregory Scot
(Hamilton, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
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Family
ID: |
40338434 |
Appl.
No.: |
12/272,967 |
Filed: |
November 18, 2008 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20090148686 A1 |
Jun 11, 2009 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60989071 |
Nov 19, 2007 |
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Current U.S.
Class: |
604/359; 604/367;
604/360 |
Current CPC
Class: |
A61L
15/46 (20130101); Y10T 428/31971 (20150401); A61L
2300/11 (20130101); Y10T 428/249953 (20150401) |
Current International
Class: |
A61F
13/15 (20060101) |
Field of
Search: |
;604/359,360,367 |
References Cited
[Referenced By]
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Primary Examiner: Stephens; Jacqueline F.
Attorney, Agent or Firm: Alexander; Richard L. Foust; Amy M.
Lopez; Abbey A.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application
No. 60/989,071, filed Nov. 19, 2007, the substance of which is
incorporated herein by reference.
Claims
What is claimed is:
1. An absorbent article comprising: a topsheet; a backsheet; an
absorbent core between the topsheet and backsheet; an odor control
system in solid form, the odor control system comprising: a) a
source of hydrogen peroxide; and b) a bleach activator capable of
reacting with hydrogen peroxide to form a peracid.
2. The absorbent article of claim 1, wherein the source of hydrogen
peroxide is selected from the group consisting of sodium
percarbonate, sodium perborate, and combinations thereof.
3. The absorbent article of claim 1, wherein the bleach activator
is selected from the group consisting of tetraacetyl ethylene
diamine (TAED), benzoylcaprolactam (BzCL),
4-nitrobenzoylcaprolactam, 3-chlorobenzoyl-caprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate
(NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate
(C.sub.10-OBS), benzoylvalerolactam (BZVL),
octanoyloxybenzenesulphonate (C.sub.8-OBS), 4-[N-(nonaoyl)amino
hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS),
dodecanoyloxybenzenesulphonate (LOBS or C.sub.12-OBS),
10-undecenoyloxybenzenesulfonate (UDOBS or C.sub.11-OBS with
unsaturation in the 10 position), and decanoyloxybenzoic acid
(DOBA) perhydrolyzable esters, and mixtures thereof.
4. The absorbent article of claim 1, wherein a leaving group (L) of
the bleach activator is selected from the group consisting of
oxybenzenesulfonate (OBS), oxybenzoic acid (OBA), and valerolactam
(VL).
5. The absorbent article of claim 1, wherein the bleach activator
is sodium nonanoyloxybenzenesulfonate (NOBS).
6. The absorbent article of claim 1, wherein the mole ratio of the
hydrogen peroxide (neat or as delivered from the peroxygen source)
to the bleach activator in the present invention ranges from at
about 100:1 to about 1:1.
7. The absorbent article of claim 1, wherein the bleach activator
is present at a level of from about 0.005 g to about 0.2 g.
8. The absorbent article of claim 1, wherein the bleach activator
is present at a level of from about 0.001 g to about 0.05 g.
9. The absorbent article of claim 1, wherein the bleach activator
is present at a level of from about 0.005 g to about 1.0 g.
10. The absorbent article of claim 1, wherein the bleach activator
is present at a level of from about 0.01 g to about 0.05 g.
11. The absorbent article of claim 1, wherein the source of
hydrogen peroxide and bleach activator is in the form of a
co-particle.
12. The absorbent article of claim 1, further comprising an agent
selected from the group consisting of an organic peroxide, a diacyl
peroxide, a metal containing bleach catalyst, a bleach boosting
compound, a preformed peracid, and mixtures thereof.
13. The absorbent article of claim 1, further comprising a perfume
raw material.
14. The absorbent article of claim 13, further comprising an agent
selected from the group consisting of absorbing gelling materials,
silicas, zeolites, carbons, starches, chelating agents, pH buffered
materials, cyclodextrine and derivatives thereof, chitin,
kieselguhr, clays, ion exchange resins, hydrophobic porous
polymers, carbonates, bicarbonates, phosphates, sulphates,
carboxylic acids, zinc salts, transition metals and combination
thereof.
15. The absorbent article of claim 1, wherein the source of
hydrogen peroxide and the bleach activator are provided within the
absorbent article such that they do not come in contact with a
body-facing surface of the topsheet.
16. The absorbent article of claim 1, wherein the odor control
system is disposed in the core, and wherein a preformed peracid is
disposed in the core.
17. The absorbent article of claim 1, wherein the source of
hydrogen peroxide and bleach activator are in the form of a
multiple particle mixture.
18. The absorbent article of claim 17, wherein the bleach activator
particle comprises, based on total particle weight, no more than 20
weight percent of any bleach activator active.
19. The absorbent article of claim 1, further comprising an agent
selected from the group consisting of absorbing gelling materials,
silicas, zeolites, carbons, starches, chelating agents, pH buffered
materials, cyclodextrine and derivatives thereof, chitin,
kieselguhr, clays, ion exchange resins, hydrophobic porous
polymers, carbonates, bicarbonates, phosphates, sulphates,
carboxylic acids, zinc salts, transition metals and combinations
thereof.
20. An absorbent article comprising: a topsheet; a backsheet; an
absorbent core between the topsheet and backsheet; an odor control
system in solid form, the odor control system comprising: a) a
peroxygen bleaching compound; and b) a bleach activator capable of
reacting with hydrogen peroxide to form a peracid.
Description
FIELD OF INVENTION
The present disclosure generally relates to bleach activator
systems and methods for incorporating such systems into disposable
absorbent articles.
BACKGROUND OF THE INVENTION
Absorbent articles, such as disposable diapers, sanitary napkins,
pantiliners, incontinence pads, tampons, and the like are typically
utilized for absorbing body fluids such as urine, feces, vaginal
fluids, and menses. Upon absorbing these fluids, the absorbent
articles can be found to contain a number of volatile chemical
compounds that include fatty acids (e.g., isovaleric acid), sulfur
containing compounds (e.g., mercaptans and sulfides), ammonia,
amines (e.g., triethylamine), ketones (e.g., 4-heptanone),
alcohols, and aldehydes (decanal) which contribute to the
unpleasant odors which can be released from these products during
wear or upon disposal. The compounds may be present in the bodily
fluids or may develop over time by chemical reaction and/or fluid
degradation mechanisms once the fluid has been absorbed into the
absorbent article. In addition, once the bodily fluids have been
absorbed into the absorbent article, they usually come in contact
with microorganisms and/or enzymes that can also generate
malodorous by-products as a result of degradation mechanisms such
as putrefactive degradation, acid degradation, protein degradation,
fat degradation, and the like. These odors can lead to unpleasant
experiences for the wearer of the absorbent article and caregiver
alike and can make the discreet use and/or disposal of the
absorbent articles difficult.
Various odor control materials, agents, techniques, and systems
have been disclosed in the art to combat some of the unpleasant
odors referred to above, including masking (i.e., covering the odor
with a perfume), absorbing the odor already present in the bodily
fluids and those generated after degradation, or preventing the
formation of the odor. Most of the focus in the prior art is on
odor adsorption technology. Examples of these types of compounds
include activated carbons, clays, zeolites, silicates, absorbing
gelling materials, starches, cyclodextrin, ion exchange resins, and
various mixtures thereof (see, for example, EP-A-348 978, EP-A-510
619, WO 91/12029, WO 91/11977, WO 89/02698, and/or WO 91/12030).
Odor control systems of the prior art are one-dimensional. For
instance, mechanisms where the malodorous compounds and their
precursors are physically adsorbed by odor control agents, and
thereby hindered from exiting the articles, are not completely
effective as the formation of the odor itself is not prevented, and
thus odor detection is not completely avoided. Additionally,
fragrances are typically used within absorbent articles to enhance
the user experience with the product (e.g., fresh-scent bursts).
These fragrances are often added at low levels and provide only a
marginal odor control benefit over the entire use cycle of the
product. Further, adsorbent technologies (e.g., activated carbon)
are often not compatible with fragrances because they can be
adsorbed and removed from the absorbent article by the adsorbent
technologies of the prior art. Thus, although prior art odor
control materials provide some control of odors associated with
bodily fluids, there still exists a need to provide
multidimensional and compatible odor control agents and
systems.
It is an object of the present invention to provide effective odor
control over a wider range of malodorous compounds and to provide
that odor control benefit in instances when fragrance may be
present in the absorbent article. Additionally, it is an object of
the present invention to provide disposable absorbent articles
which provide multiple mechanisms for combating odor, including,
but not limited to, reacting with the odor causing molecules and
preventing the formation of malodors.
It has been found that the objects of the present inventions are
accomplished by using a bleach activator system. An embodiment of a
bleach activator system of the present invention is a combination
of sodium percarbonate and sodium nonanoyloxybenzenesulfonate
(NOBS), which is capable of generating a peroxyacid in-situ within
a disposable absorbent article to control malodor.
The laundry industry developed a class of materials known as
"bleach activators". Bleach activators, typically perhydrolyzable
acyl compounds having a leaving group such as oxybenzenesulfonate
(OBS), react with the active oxygen group, typically hydrogen
peroxide or its anion, to form a more effective peroxyacid oxidant.
In the laundry context, it is the peroxyacid compound which then
oxidizes the stained or soiled substrate. While hydrogen peroxide
at modest concentrations can bleach effectively at temperatures of
about 60.degree. C. and above, use of bleach activators enables
effective bleaching at significantly lower temperatures. Numerous
substances have been disclosed in the art as effective bleach
activators. One widely-used bleach activator is tetraacetyl
ethylene diamine (TAED). Another type of activator, such as
nonanoyloxybenzenesulfonate (NOBS) and other activators which
generally comprise long chain alkyl moieties, yields a peracid that
is hydrophobic in nature and provides excellent performance on
dingy stains
Surprisingly, bleach activator systems that generate in-situ
peroxyacids can be used in absorbent articles for significantly
decreasing bodily odor. These results are evident when absorbent
articles comprising a bleach activator system of the present system
are compared to the same absorbent article not having the bleach
activator system. While not wishing to be bound to theory, it is
speculated that the peroxyacids formed in-situ according to the
present invention have a dual odor control mechanism: first, they
prevent the generation of odor in the absorbent article by blocking
enzymatic and/or microbial activity; and second, they combat the
odors already present in the absorbent article by oxidizing them
into non-odiferous molecules.
In contrast to the use of pre-formed peroxyacids of the prior art,
bleach activator systems of the present invention generate the
reactive odor control agents only when they are most needed in the
absorbent article (i.e., at the time of collection of the waste
bodily fluid (e.g., urine, menstrual fluid, and runny bowel
exudates)). This is advantageous with reactive materials such as
peroxyacids because it lessens the possibility that the material
will prematurely react with other materials found in the absorbent
article prior to use and it increases the likelihood that the
reactive odor control agents are available when needed (e.g., post
urine insult). In this way, bleach activator systems of the present
invention comprise precursor peroxyacids that are activatable.
Additionally, in-situ generation of peroxyacids via bleach
activator systems described herein offers the distinct advantage
that they can be used in the presence of a wide variety of
fragrance materials. Because formation of the peroxyacid is
generated by the bleach activator system upon contact with aqueous
media, significant reductions in the concentration of the perfume
raw materials prior to insult (due to incompatibility with the
peroxyacid or adsorption on the surface of the odor control media)
is avoided and enables the fragrance to enhance the overall product
experience, especially upon initial opening of the product
packaging.
An additional advantage of the in-situ generated peroxyacids of the
present invention is that the generation of malodorous smelling
by-products like chlorine derivatives and ammonium derivatives is
avoided when they come into contact with bodily fluids. In contrast
to the in-situ generated peroxyacids of the present invention,
oxidants like persulphate, periodate, percarbonate, and/or
perborate oxidize the chlorides usually present in bodily fluids
into chlorine derivatives that are not acceptable to the consumer
from an odor point of view. Also in contrast to the in-situ
generated peroxyacids of the present invention, oxidants like urea
peroxides, calcium peroxides, strontium peroxides and/or barium
peroxides (i.e., compounds having an alkaline pH) promote the
formation of malodorous ammonia derivatives (i.e., one of the
by-products of proteins degradation occurring in the bodily fluids
when they come into contact with it).
SUMMARY OF THE INVENTION
The present invention relates to an absorbent article comprising a
topsheet, a backsheet, an absorbent core between the topsheet and
backsheet, and an odor control system. The odor control system may
comprise a bleach activator system. The bleach activator system may
comprise a peroxygen bleaching compound and a bleach activator
capable of reacting with the peroxygen bleaching compound to form a
peracid. The peroxygen bleaching compound may be a source of
hydrogen peroxide.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an example Headspace GC/MS analysis of an aged urine
loaded control (blank) diaper.
FIG. 2 is an example Headspace GC/MS analysis of an aged urine
loaded diaper comprising sodium percarbonate alone (See Example
5).
FIG. 3 is an example Headspace GC/MS analysis of an aged urine
loaded diaper comprising a multiple particle bleach activator odor
control system (See Example 4).
FIG. 4 is a side view of a headspace sample vessel.
DETAILED DESCRIPTION OF THE INVENTION
The disposable absorbent articles according to the present
invention may comprise an odor control system. The odor control
system may comprise a bleach activator system. The bleach activator
system may comprise a peroxygen bleaching compound and a bleach
activator described herein after.
The Peroxygen Bleaching Compound
The peroxygen bleaching compounds of the present invention include
those capable of yielding hydrogen peroxide in aqueous liquor.
Hydrogen peroxide sources are described in detail in Kirk Othmer's
Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley &
Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)," and include
the various forms of sodium perborate and sodium percarbonate,
including various coated and modified forms.
The sources of hydrogen peroxide of the present invention may
include any convenient source, including hydrogen peroxide itself.
For example, perborate, e.g., sodium perborate (any hydrate
including the mono- or tetra-hydrate), sodium carbonate
peroxyhydrate or equivalent percarbonate salts, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
may be used. Also useful are sources of available oxygen such as
persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium
perborate monohydrate and sodium percarbonate are further examples.
Other useful sources of hydrogen peroxide include stable complexes
of polyvinylpyrrolidone with hydrogen peroxide (as disclosed in
U.S. Patent App. No. 2006/0292091 and available from International
Specialty Products, N.J. under the tradename Peroxydone) and stable
crystalline complexes of carbohydrate and hydrogen peroxide (as
disclosed in U.S. Pat. No. 6,887,496. Mixtures of any hydrogen
peroxide sources can also be used.
A percarbonate bleach may comprise dry particles having an average
particle size in the range from about 500 micrometers to about
1,000 micrometers, not more than about 10% by weight of the
particles being smaller than about 200 micrometers and not more
than about 10% by weight of the particles being larger than about
1,250 micrometers. Optionally, the percarbonate can be coated with
a silicate, borate or water-soluble surfactants. Sodium
Percarbonate, available from OCI Chemical Corp, Decatur, Ala. under
the tradename Provox C or Kemira Kemi AB, Sweden under the
tradename ECOX-C, can be in uncoated or coated form, and can be
used in the present invention.
The Bleach Activator
The peroxygen bleach compound may be formulated with a bleach
activator. The bleach activator may be considered a "peracid
precursor." The bleach activator may be present within the
absorbent article at levels from about 0.001 g, from about 0.005 g,
from about 0.01 g to about 0.05 g, to about 0.2 g, to about 1.0 g
per absorbent article. The bleach activator may include any
compound, which when used in conjunction with a hydrogen peroxide
source, results in the in-situ production of a peracid
corresponding to the bleach activator. Examples of bleach
activators are disclosed in U.S. Pat. Nos. 5,576,282; 4,915,854;
and 4,412,934. U.S. Pat. No. 4,634,551 also discloses peroxygen
bleaching compounds and bleach activators of the present
invention.
Bleach activators may include tetraacetyl ethylene diamine (TAED),
benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam,
3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS),
nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz),
decanoyloxybenzenesulphonate (C.sub.10-OBS), benzoylvalerolactam
(BZVL), octanoyloxybenzenesulphonate (C.sub.8-OBS), perhydrolyzable
esters and mixtures thereof, and benzoylcaprolactam and
benzoylvalerolactam. Bleach activators that have an OBS or VL
leaving group may be used in the present invention.
Hydrophobic bleach activators may be used and may include,
nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) amino
hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an example
of which is described in U.S. Pat. No. 5,523,434,
dodecanoyloxybenzenesulphonate (LOBS or C.sub.12-OBS),
10-undecenoyloxybenzenesulfonate (UDOBS or C.sub.11-OBS with
unsaturation in the 10 position), and decanoyloxybenzoic acid
(DOBA).
Bleach activators of the present invention are also described in
U.S. Pat. Nos. 5,698,504; 5,695,679; 5,686,401; 5,686,014;
5,405,412; 5,405,413; 5,130,045; 4,412,934; and U.S. Ser. Nos.
08/709,072; and 08/064,564.
The mole ratio of hydrogen peroxide (neat or as delivered from the
peroxygen source) to bleach activator in the present invention may
range from at about 100:1 to 1:1; from about 80:1 to 5:1, and from
about 70:1 to about 20:1.
Quaternary substituted bleach activators (QSBAs) and quaternary
substituted peracids (QSPs) may also be used. QSBA structures are
further described in U.S. Pat. Nos. 5,686,015; 5,654,421;
5,460,747; 5,584,888; and 5,578,136.
Also, bleach activators of the present invention may include ones
that are amide-substituted as described in U.S. Pat. Nos.
5,698,504; 5,695,679; and 5,686,014. Examples of such bleach
activators include: (6-octanamidocaproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate,
(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
Other useful bleach activators that may be used in the present
invention are disclosed in U.S. Pat. Nos. 5,698,504; 5,695,679;
5,686,014; and 4,966,723. Included in one or more of these patents
is benzoxazin-type activators, such as a C.sub.6H.sub.4 ring to
which is fused in the 1,2-positions a moiety
--C(O)OC(R.sup.1).dbd.N--.
Nitriles, such as acetonitriles and/or ammonium nitriles and other
quaternary nitrogen containing nitriles, are another class of
bleach activators that may be useful in the present invention.
Nitrile bleach activators are described in U.S. Pat. Nos.
6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315;
5,741,437; 5,739,327; and 5,004,558, as well as EP Nos. 790 244;
775 127; 1 017 773; 1 017 776, and, finally as described in WO Nos.
99/14302; 99/14296; and WO96/40661.
Acyl lactam bleach activators, as described in U.S. Pat. Nos.
5,698,504; 5,695,679; and 5,686,014 may be used in the present
invention. For example, acyl caprolactams (see WO 94-28102) and
acyl valerolactams (see U.S. Pat. No. 5,503,639) may be used.
Further, sodium nonanoyloxybenzenesulfonate, available from Future
Fuel Company, Batesville, Ark. may be used as a bleach activator in
the present invention. The absorbent article of the present
invention may comprise a single class of bleach activator compounds
or it may comprise a combination of bleach activator compounds.
Optional Agents
The absorbent articles of the present invention may further
comprise, in addition to the bleach activator systems described
herein, other conventional bleaching agents and dispersants, or
mixtures thereof.
Organic Peroxides may be used in the present invention, including
Diacyl Peroxides, which are illustrated in Kirk Othmer,
Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons,
1982 at pages 27-90 and especially at pages 63-72.
Metal-containing Bleach Catalysts may be used in the present
invention, including manganese and cobalt-containing bleach
catalysts. One type of metal-containing bleach catalyst is a
catalyst system comprising a transition metal cation of defined
bleach catalytic activity, such as copper, iron, titanium,
ruthenium tungsten, molybdenum, or manganese cations, an auxiliary
metal cation having little or no bleach catalytic activity, such as
zinc or aluminum cations, and a sequestrate having defined
stability constants for the catalytic and auxiliary metal cations,
ethylenediaminetetraacetic acid, ethylenediaminetetra
(methylenephosphonic acid) and water-soluble salts thereof. Such
catalysts are disclosed in U.S. Pat. No. 4,430,243.
Manganese Metal Complexes may be used in the present invention,
including the manganese-based catalysts disclosed in U.S. Pat. Nos.
5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and
European Pat. App. Pub. Nos. 549,271 A1; 549,272 A1; 544,440 A2;
and 544,490 A1. Examples of these catalysts include
Mn.sup.IV.sub.2(u-O).sub.3(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2-
(PF.sub.6).sub.2,
Mn.sup.III.sub.2(u-O).sub.1(u-OAc).sub.2(1,4,7-trimethyl-1,4,7-triazacycl-
ononane).sub.2(ClO.sub.4).sub.2,
Mn.sup.IV.sub.4(u-O).sub.6(1,4,7-triazacyclononane).sub.4(ClO.sub.4).sub.-
4,
Mn.sup.IIIMn.sup.IV.sub.4(u-O).sub.1(u-OAc).sub.2-(1,4,7-trimethyl-1,4,-
7-triazacyclononane).sub.2(ClO.sub.4).sub.3,
Mn.sup.IV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH.sub.3).sub.3(PF.s-
ub.6), and mixtures thereof. Other metal-based bleach catalysts may
include those disclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611.
The use of manganese with various complex ligands to enhance
bleaching is also reported in U.S. Pat. Nos. 4,728,455; 5,284,944;
5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and
5,227,084.
Cobalt Metal Complexes may be used in the present invention,
including those describe in U.S. Pat. Nos. 5,597,936; 5,595,967;
and 5,703,030; and in M. L. To be, "Base Hydrolysis of
Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983),
2, pages 1-94. Examples include cobalt pentaamine acetate salts
having the formula [Co(NH.sub.3).sub.5OAc] T.sub.y, wherein "OAc"
represents an acetate moiety and "T.sub.y" is an anion, and
especially cobalt pentaamine acetate chloride,
[Co(NH.sub.3).sub.5OAc]Cl.sub.2; as well as
[Co(NH.sub.3).sub.5OAc](OAc).sub.2;
[Co(NH.sub.3).sub.5OAc](PF.sub.6).sub.2; [Co(NH.sub.3).sub.5OAc]
(SO.sub.4); [Co(NH.sub.3).sub.5OAc] (BF.sub.4).sub.2; and
[Co(NH.sub.3).sub.5OAc] (NO.sub.3).sub.2 (herein "PAC").
Iron Metal Complexes may be used in the present invention,
including those describe in U.S. Pat. Nos. 6,302,921; 6,287,580;
6,140,294; 5,597,936; 5,595,967; 4,810,410 and 5,703,030; and in J.
Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and
Characterization of Inorganic Compounds, W. L. Jolly
(Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502
(1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18,
2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of
Physical Chemistry, 56, 22-25 (1952). Transition Metal Complexes of
Macropolycyclic Rigid may be used in the present invention.
Transition-metal bleach catalysts of Macrocyclic Rigid Ligands
which are suitable for use in the invention compositions may
include the following:
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) Hexafluorophosphate
Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) Hexafluorophosphate
Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Hexafluorophosphate
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) Tetrafluoroborate Dichloro-5,12-dimethyl-1,5,8,12
tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate
Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(M) Hexafluorophosphate
Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II).
Bleach Boosting Compounds may be used in the present invention and
may comprise one or more bleach boosting compounds. Bleach boosting
compounds provide increased bleaching effectiveness in lower
temperature applications. The bleach boosters act in conjunction
with conventional peroxygen bleaching sources to provide increased
bleaching effectiveness. This is normally accomplished through
in-situ formation of an active oxygen transfer agent such as a
dioxirane, an oxaziridine, or an oxaziridinium. Alternatively,
preformed dioxiranes, oxaziridines and oxaziridiniums may be
used.
Among suitable bleach boosting compounds for use in the present
invention are cationic imines, zwitterionic imines, anionic imines
and/or polyionic imines having a net charge of from about +3 to
about -3, and mixtures thereof. These imine bleach boosting
compounds of the present invention include those of the general
structure:
##STR00001##
where R.sup.1-R.sup.4 may be a hydrogen or an unsubstituted or
substituted radical selected from the group consisting of phenyl,
aryl, heterocyclic ring, alkyl and cycloalkyl radicals.
Bleach boosting compounds may include zwitterionic bleach boosters,
which are described in U.S. Pat. Nos. 5,576,282 and 5,718,614.
Other bleach boosting compounds include cationic bleach boosters
described in U.S. Pat. Nos. 5,360,569; 5,442,066; 5,478,357;
5,370,826; 5,482,515; and 5,550,256, as well as WO App. Nos.
95/13351; 95/13352; and 95/13353.
The bleach boosting compounds, when present, may be employed in
conjunction with the peroxygen bleaching compound in the bleach
activator systems of the present invention.
Dispersant aids/binders may be used in the present invention. These
materials may be used to aid in distributing the bleach activator
systems through out the entire core of the absorbent article while
also aiding in keeping the peroxygen bleaching compound and bleach
activator closely associated with one another. These dispersant
aids may have low melting solids to enable mixing with the bleach
activator materials and may be hydrophilic to provide sufficient
wetting and activation of the peroxygen bleach compounds.
Dispersant aids may include glucose, sorbitol, maltose, glucamine,
sucrose, polyvinyl alcohol, starch, alkyl polyglycoside, sorbitan
fatty ester, polyhydroxy fatty acid amides containing from about 1
to about 18 carbon atoms in their fatty acid moieties, and mixtures
thereof. Dispersant aids may also include a polyethylene glycol
polymer available from The Dow Chemical Company, Midland Mich.
under the tradename Carbowax.
Additional odor control materials may be used in the present
invention. These materials may be classified according to the type
of odor the agent is intended to combat. Odors may be chemically
classified as being acidic, basic, or neutral. Alternatively, the
odor control agents may be categorized with respect to the
mechanism by which the malodor detection is reduced or prevented.
For example, odor control agents that chemically react with
malodorous compounds or with compounds that produce malodorous
degradation products thereby generating compounds lacking odor or
having an odor acceptable to consumers may also be used. For
instance, carbonates (e.g., sodium carbonate), bicarbonates (e.g.,
sodium bicarbonate), phosphates (e.g., sodium phosphate), sulphates
(e.g., zinc and copper sulphates), carboxylic acids such as citric
acid, lauric acid, boric acid, adipic acid and maleic acid, zinc
salts of carboxylic acids such as zinc ricinoleate, transition
metals, activated carbons, clays, zeolites, silicas, superabsorbent
polymers, and starches may be used. Such odor control agents and
systems are disclosed in EP-A-348 978; EP-A-510 619; WO 91/12029;
WO 91/11977; WO 91/12030; WO 81/01643; and WO 96/06589.
Chelating agents may also be used and may include amino
carboxylates such as ethylenediamine-tetracetate (described in U.S.
Pat. No. 4,356,190), amino phosphonates such as
ethylenediaminetetrakis (methylene-phosphonates), and
polyfunctionallysubstituted aromatic chelating agents (described in
U.S. Pat. No. 3,812,044).
Another suitable odor control agent that may be used in the present
invention is a buffer system, such as citric acid and sodium
bicarbonate, sodium phosphate and sorbic acid buffer systems. Also,
buffer systems having a pH of from 7 to 10 (described in WO
94125077) may be used.
Ion exchange resins, such as those described in U.S. Pat. Nos.
4,289,513 and 3,340,875 may also be used as odor control agents, as
well as hydrophobic porous polymers, including those described in
WO2005/120594. Masking agents, such as perfumes, may also be used
as odor control agents.
Preformed Peracids may be used in addition to the bleach activator
systems of the present invention. The preformed peracid compound
may include any convenient compound that is stable and that, under
consumer use conditions, provides an effective amount of peracid or
peracid anion. The preformed peracid compound may include
percarboxylic acids and salts, percarbonic acids and salts,
perimidic acids and salts, peroxymonosulfuric acids and salts, and
mixtures thereof. Examples of these are described in U.S. Pat. No.
5,576,282.
One class of suitable organic peroxycarboxylic acids of the present
invention may have the general formula:
##STR00002## wherein R is an alkylene or substituted alkylene group
containing from 1 to about 22 carbon atoms or a phenylene or
substituted phenylene group, and Y is hydrogen, halogen, alkyl,
aryl, --C(O)OH or --C(O)OOH.
Organic peroxyacids suitable for use in the present invention can
contain either one or two peroxy groups and can be either aliphatic
or aromatic. When the organic peroxycarboxylic acid is aliphatic,
the unsubstituted peracid has the general formula:
##STR00003## where Y can be, for example, H, CH.sub.3, CH.sub.2Cl,
C(O)OH, or C(O)OOH; and n is an integer from 0 to 20. When the
organic peroxycarboxylic acid is aromatic, the unsubstituted
peracid has the general formula:
##STR00004## wherein Y can be, for example, hydrogen, alkyl,
alkylhalogen, halogen, C(O)OH or C(O)OOH.
Monoperoxy acids useful herein include alkyl and aryl peroxyacids
such as: (i) peroxybenzoic acid and ring-substituted peroxybenzoic
acid, e.g., peroxy-a-naphthoic acid, monoperoxyphthalic acid
(magnesium salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic
acid (sodium salt); (ii) aliphatic, substituted aliphatic and
arylalkyl monoperoxy acids, e.g., peroxylauric acid, peroxystearic
acid, N-nonanoylaminoperoxycaproic acid (NAPCA),
N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and
N,N-phthaloylaminoperoxycaproic acid (PAP); and (iii)
amidoperoxyacids, e.g., monononylamide of either peroxysuccinic
acid (NAPSA) or of peroxyadipic acid (NAPAA).
Diperoxyacids useful herein include alkyl diperoxyacids and
aryldiperoxyacids, such as: (i) 1,12-diperoxydodecanedioic acid;
(ii) 1,9-diperoxyazelaic acid; (iii) diperoxybrassylic acid;
diperoxysebacic acid and diperoxyisophthalic acid; (iv)
2-decyldiperoxybutane-1,4-dioic acid; and (v)
4,4'-sulfonylbisperoxybenzoic acid.
Such bleaching agents are disclosed in U.S. Pat. Nos. 4,483,781;
4,412,934; 4,634,551; and European Patent Application 0,133,354.
Sources may also include 6-nonylamino-6-oxoperoxycaproic acid,
described in U.S. Pat. No. 4,634,551. Persulfate compounds
(including OXONE, manufactured commercially by E.I. DuPont de
Nemours of Wilmington, Del.) can also be employed as a suitable
source of peroxymonosulfuric acid. PAP is disclosed in, for
example, U.S. Pat. Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757;
and 5,132,431.
Bleach Activator System as a Co-Particle
The peroxygen bleaching compounds and bleach activator materials of
the present invention can be incorporated into the absorbent
articles by any means or in any form that allows in-situ generation
of the peroxyacid. This could include the addition of the two
materials added separately or as a premixed solid to the absorbent
article. For instance, the peroxygen bleaching compound and bleach
activator may be delivered to the absorbent article as a
co-particle composition through the use of a dispersant aid/binder
material as disclosed herein or as disclosed in WO 2007/127641.
Bleach Activator System as a Multiple Particle Mixture
The peroxygen bleaching compound and bleach activator may also be
delivered to the absorbent article as a mixture of particles. For
instance, the bleach activator may be in the form of an extrudate
as disclosed in U.S. Pat. Nos. 4,486,327 and 6,617,300 and then
mixed with a peroxygen bleaching compound to provide a multiple
particle bleach activator system. Additionally, in another
embodiment of the present invention, the bleach activator may be
coated onto a core particle through the use of suitable binders and
coating materials as disclosed in WO 2005/080542 and then mixed
with an appropriate amount of peroxygen bleaching compound to
provide a multiple particle bleach activator system.
Suitable core materials used to make the bleach activator particle
include, but are not limited to, ingredients such as sodium
sulfate, sodium carbonate and sodium phosphate, as well as
composite detergent ingredient compositions made by processes such
as spray-drying, agglomeration, compaction, and/or extrusion
processes. Examples of such composite compositions include
particles/granules comprising detergent builder, surfactant and,
optionally, polymer ingredients. Suitable core materials may have a
particle size that is comparable to the peroxygen bleach compound
to provide proper mixing between the peroxygen bleach compound and
the bleach activator particle and may have a particle size that
will range from about 200-1300 .mu.m and may have an average
particle size from about 500-1000 .mu.m. While suitable cores, such
as detergent particles/granules, are typically made as an
intermediate within a detergent production facility, suitable cores
and core raw materials can be obtained from FMC Corporation of
Philadelphia, Pa., U.S.A.; Jost Chemicals of St. Louis, Mo.,
U.S.A.; General Chemical Corporation of Parsippany, N.J., U.S.A;
and Mallinckrodt Baker of Phillipsburg, N.J., USA. Additionally,
superabsorbent polymers may also be used as suitable core
components and can be obtained from BASF of Ludwigshafen, Germany;
Nippon Shokubai of Osaka, Japan; and Evonik Degussa of Dusseldorf,
Germany. Further, suitable core materials can be chosen from
polymeric particles, inorganic salts, clays, mica, starches,
sugars, zeolites, silicon dioxide and inorganic coordination
complexes.
Suitable binder materials used to make the bleach activator
particle include materials selected from the group consisting of
polymers, surfactants, solvents, and mixtures thereof. Examples of
polymers include sodium polyacrylate, acrylic-maleic co-polymers,
polyethylene glycol, polyvinyl acetate, polyvinyl pyrrolidone,
cellulose ethers, and hydroxypropyl cellulose. Examples of
surfactants include anionic, cationic, zwitterionic and nonionic
surfactants. Examples of solvents include water, alcohols, linear
alcohols, branched alcohols, and fatty alcohols. Suitable binders
can be obtained from BASF of Ludwigshafen, Germany; Dow Chemical
Company of Midland, Mich., U.S.A.; Hercules Incorporated of
Wilmington, Del., U.S.A.; Shell Chemical LP of Houston, Tex.,
U.S.A.; Procter & Gamble Chemicals of Cincinnati, Ohio, U.S.A.;
and Rohm and Hass Company of Philadelphia, Pa., U.S.A.
Suitable solid coating aids used to make the bleach activator
particle include materials selected from the group consisting of
acetates, sulfates, carbonates, borates, phosphates, and mixtures
thereof. Examples of acetates include magnesium acetate,
Mg(CH.sub.3COO).sub.2; and sodium acetate, NaCH.sub.3COO. Examples
of sulfates include magnesium sulfate, MgSO.sub.4; and sodium
sulfate, Na.sub.2SO.sub.4. Examples of carbonates include sodium
carbonate, Na.sub.2CO.sub.3; potassium carbonate, K.sub.2CO.sub.3.
Examples of borates include sodium borate, Na.sub.2B4O.sub.7.
Examples of phosphates include sodium phosphate dibasic,
Na.sub.2HPO.sub.4; and sodium tripolyphosphate, Na.sub.5P.sub.3OIO.
Such coating aids may be introduced to the coating process as
substantially anhydrous salts. While not being bound by theory, it
is believed that their conversion to stable hydrate phases provides
a mechanism for the removal of binder moisture and enables
processing without the requirement of a drying step. Suitable solid
coating aids can be obtained from PQ Corporation of Valley Forge,
Pa., U.S.A.; FMC Corporation of Philadelphia, Pa., U.S.A.; and
Mallinckrodt Baker, Inc. of Phillipsburg, N.J., U.S.A.
In addition, the bleach activator particle may also optionally
comprise dyes and pigments for the purpose of conveying a signal to
the caregiver. The signal may communicate the presence of the
bleach activator particle. Non-limiting examples of dyes and
pigments include organic and inorganic pigments, aqueous and other
solvent-soluble dyes. Such dyes and pigments can be obtained from
Ciba Specialty Chemicals Corporation of Newport, Del., U.S.A.;
Clariant Corporation of Charlotte, N.C., U.S.A.; and Milliken
Chemical Company of Spartanburg, S.C., U.S.A. Suitable equipment
for performing the particle making processes disclosed herein
includes paddle mixers, ploughshare mixers, ribbon blenders,
vertical axis granulators, and drum mixers, both in batch and,
where available, in continuous process configurations. Such
equipment can be obtained from Lodige GmbH (Paderborn, Germany),
Littleford Day, Inc. (Florence, Ky., U.S.A.), Forberg AS (Larvik,
Norway), Glatt Ingenieurtechnik GmbH (Weimar, Germany). Further,
the bleach activator particle may also optionally be dried to
remove any moisture prior to being mixed with the peroxygen bleach
compound of the multiple particle bleach activator system.
In one aspect of the present invention, said bleach activator
particle comprises, based on total particle weight, no more than
about 50 weight percent of any bleach activator, no more than about
20 weight percent of any bleach activator active, no more than
about 10 weight percent of any bleach activator active, or no more
than about 5 weight percent of any bleach activator active.
The multiple particle bleach activator system of the present
invention may be formed by mixing the peroxygen bleach compound
with the bleach activator particle. Suitable equipment for
performing the mixing process includes, but is not limited to
paddle mixers, such as a Forberg mixer and rotating drum
mixers.
Absorbent Article
The disposable absorbent articles of the present invention may
comprise a topsheet having a garment facing surface and a body
facing surface, a backsheet having a garment facing surface and a
body facing surface, and an absorbent core disposed between said
body facing surface of the backsheet and the garment facing surface
of the topsheet.
In certain embodiments, the absorbent articles may take the form of
a diaper, a pant product, an adult incontinence product, or a
feminine hygiene product, e.g., a sanitary napkin or panty liner.
Given these various product forms, additional components may also
exist within the disposable absorbent article. Such components may
be selected from the group consisting of an outer cover, side
panels, a cuff, an elastic feature, a wing, a fastening system, and
combinations thereof.
Absorbent Core
The articles of the present disclosure may additionally comprise
one or more absorbent cores. The absorbent core is at least
partially disposed between the topsheet and the backsheet and may
take on any size or shape that is compatible with the disposable
absorbent article. Exemplary absorbent structures for use as the
absorbent core of the present invention that have achieved wide
acceptance and commercial success are described in U.S. Pat. Nos.
4,610,678; 4,673,402; 4,888,231; and 4,834,735; and U.S. Pub. Nos.
2005-0273071, 2005-0171499, 2007-0191806, 2004-0162538, and
2005-0095942. The absorbent core may further comprise the dual core
system containing an acquisition/distribution core of chemically
stiffened fibers positioned over an absorbent storage core as
detailed in U.S. Pat. Nos. 5,234,423 and 5,147,345.
As discussed herein "absorbent gelling materials" and
"superabsorbent polymers" are those materials that, upon contact
with aqueous fluids, such as bodily fluids, imbibes such fluids and
form hydrogels. These absorbent gelling materials are typically
capable of absorbing large quantities of aqueous bodily fluids, and
further capable of retaining such absorbed fluids under moderate
pressures. These absorbent gelling materials are typically in the
form of discrete, nonfibrous particles. Other forms, such as
fibers, foams, sheets, strips, or other macrostructures, are also
suitable for use herein. Suitable absorbent gelling materials in
the form of open cell foams may include those disclosed in U.S.
Pat. Nos. 3,563,243; 4,554,297; 4,740,520; and 5,260,345.
In certain embodiments of the present disclosure, the absorbent
article may also include a sublayer disposed between the topsheet
and the backsheet. The sublayer may have a body facing surface and
a garment facing surface and may be any material or structure
capable of accepting, storing or immobilizing bodily exudates.
Thus, the sublayer may include a single material or a number of
materials operatively associated with each other. Further, the
sublayer may be integral with another element of the absorbent
article or may be one or more separate elements joined directly or
indirectly with one or more elements of the article. Further, the
sublayer may include a structure that is separate from the core or
may include or be part of at least a portion of the core.
Additionally, suitable absorbent cores may contain reduced amounts
of cellulosic airfelt material. For instance, such cores may
comprise less than about 40%, 30%, 20%, 10%, 5%, or even 1%. Such a
core comprises primarily absorbent gelling material in amounts of
at least about 60%, 70%, 80%, 85%, 90%, 95%, or even about 100%,
where the remainder of the core comprises a microfiber glue (if
applicable). Such cores, microfiber glues, and absorbent gelling
materials are described in U.S. Pat. Nos. 5,599,335; 5,562,646;
5,669,894; 6,790,798; and U.S. Patent Publications 2004/0158212A1
and 2004/0097895A1; and U.S. application Ser. Nos. 10/758,375 and
10/758,138.
In further embodiments, the articles according to the present
disclosure may further comprise a wetness sensation member. This
member may be disposed in various locations within the article. For
instance, the wetness sensation member may be disposed on the
topsheet. The member may comprise a permeable layer and an
impermeable layer, wherein urine passes through the permeable layer
and not through the impermeable layer such that a wearer is made of
aware of the fact that urination has occurred as a result of the
"wet" feeling. Suitable members are detailed in U.S. Pat. No.
6,627,786.
Bleach activator systems of the present invention may be
incorporated into the absorbent articles described in U.S. Pub.
Nos. 2005-0273071, 2005-0171499, 2007-0191806, 2004-0162538, and
2005-0095942. Further, bleach activator systems of the present
invention may be placed in or on the different absorbent article
components described above, including an absorbent core, an
acquisition system, barrier leg cuffs, a backsheet, and/or a
topsheet.
Further, they may be incorporated into lotions applied to the
topsheet. These lotions may be hydrophilic or hydrophobic. For
instance bleach activator systems may be suspended in the
lotion.
The effectiveness of the odor control system comprising a bleach
activator system of the present invention can be demonstrated by
determining the percent reduction in the concentration of common
odorant molecules in the headspace surrounding a urine loaded
diaper comprising said bleach activator system. The headspace
surrounding a urine loaded aged diaper can be found to contain many
odiferous compounds; and Headspace Gas Chromatography/Mass
Spectrometry analysis can be used to evaluate changes in the
presence and concentration of molecules in said headspace. In this
test, a given volume of headspace is collected from an aged urine
loaded diaper onto a Tenax trap that is then attached to an Agilent
Technologies 6890 Gas Chromatograph equipped with a HP 5973 Mass
Spectrometry detector and a Gerstel ODP Sniffport. A control diaper
(blank) containing no odor control material is analyzed along with
a diaper comprising sodium percarbonate alone (See Example 5) and a
diaper comprising the multiple particle bleach activator odor
control system (See Example 4) of the present invention. Dimethyl
disulfide and 4-Heptanone are chosen as the odorant molecules for
the analysis as they are commonly found in the headspace associated
with bodily waste products such as urine, menses, and feces. Tables
1 & 2 display the results of the Headspace GC/MS analysis as
demonstrated by the GC/MS Total ion Chromatogram Abundance for
dimethyl disulfide and 4-heptanone, respectively. The total ion
Chromatogram Abundance is representative of the molecular
concentration of the odorant molecules in the headspace and the
control diaper represents the maximum concentration of odorant
molecules present under the test conditions because it contained no
odor control system.
The diaper comprising the sodium percarbonate demonstrates an 18%
reduction in the amount of dimethyl disulfide and a 32% reduction
in the amount of 4-heptanone in the headspace as compared to the
control diaper. These results are in sharp contrast to the diaper
comprising a multiple particle bleach activator odor control system
of the present invention that more effectively reduces the
concentration of these odorants in the headspace. This diaper
demonstrates a 77% reduction in dimethyl disulfide and a 56%
reduction of 4-heptanone in the headspace as compared to the
control diaper. The ability of multiple particle bleach activator
odor control system to significantly reduce the concentration of
odorant molecules derived from urine may be advantageous in certain
embodiments of the present invention.
TABLE-US-00001 TABLE 1 Removal of Dimethyldisulfide GC/MS Total Ion
Approximate Chromatogram reduction as Test Material Abundance
compared to blank Control (Blank) 6742 -- Bleach Activator system
1513 77% (Example 4) Sodium Percarbonate 5542 18% (Example 5)
TABLE-US-00002 TABLE 2 Removal of 4-Heptanone GC/MS Total Ion
Approximate Chromatogram reduction as Test Material Abundance
compared to blank Control (Blank) 3317 -- Bleach Activator system
1455 56% (Example 4) Sodium Percarbonate 2271 32% (Example 5)
Test Methods
High Performance Liquid Chromatography (HPLC) Test for
Nonanoyloxybenzenesulfonate Bleach Activator
A suitable test method for the quantification of
Nonanoyloxybenzenesulfonate (NOBS) either from particles coated
with NOBS or an absorbent article containing such particles, is by
HPLC with UV detection. Analysis is conducted on an Waters 2695
liquid chromatograph solvent delivery system, in-line degasser,
autosampler, column heater (set at 35.degree. C.) and a photodiode
array detector and supported by Empower software for instrument
control, data collection and processing. Chromatography is
performed on a Dionex Acclaim.RTM. Polar Advantage reverse phase
column (C16 3 micron 150.times.4.6 mm Part #061318) using a binary
gradient, at 1 mL/minute flow rate, with UV detection at 220 nm.
Extraction of an absorbent article is described below. The extract
is filtered through a 0.45 micron PTFE Acrodisc CR filter before 5
.mu.L is injected for analysis.
Reagents and Solutions:
Extraction Solvent: Denatured (95%) Ethanol: Glacial Acetic
Acid:Water (40:20:40 by weight)
Bleach activator standard: Nonanoyloxybenzenesulfonate (NOBS)
powder of known activity
HPLC Eluent A--Aqueous 0.01 M Ammonium Dihydrogen Orthophosphate
(HPLC grade)
HPLC Eluent B--70:30 HPLC Grade Acetonitrile:Water (HPLC grade)
HPLC Gradient Elution Profile
TABLE-US-00003 Time Eluent A Eluent B Flow (min) (%) (%) (mL/min) 0
70 30 1.00 10 5 95 1.00 12.5 5 95 1.00 13 70 30 1.00 18 70 30
1.00
Preparation of Calibration Standards:
All standards are prepared using Class A volumetric glassware.
First, approximately 100 mg of the NOBS primary standard is
accurately weighed and transferred to a 100 mL volumetric flask,
brought to volume with the extraction solvent and mixed thoroughly.
Next, calibration standards of approximately 10, 20, 40 and 80 mg/L
are prepared by pipeting 1.0, 2.0, 4.0 and 8.0 mL of the stock
solution, each into a separate 100 mL volumetric flask, brought to
volume with the extraction solvent, and mixed thoroughly. If
needed, additional calibration standards can be prepared to assure
that the concentration of the NOBS falls within the span of the
calibration curve.
HPLC Analyses:
5 .mu.L of each calibration standard and sample is injected. The
integrated peak areas for the calibration standards are used to
prepare a calibration curve of Response (peak area) verses
Concentration from which the concentration of NOBS can be
calculated. Report results to +0.1 mg/mL. This value can be used to
calculate the weight % of NOBS on a particle or the total NOBS
extracted from an absorbent article. weight %=measured NOBS
concentration (mg/L)*dissolution volume (L)/particle mass (mg)*100
mg/diaper=measured NOBS concentration (mg/L)*extraction volume
(L)/diaper Results are reported to .+-.0.1% or +0.1 mg/diaper.
Reflectoquant Peroxide Test
Equipment:
Reflectoquant Meter; RQflex 10, available from EMD Chemicals
Peroxide Test Strips; stock number 16974; measuring 0.2-20.0 mg/mL
concentration range
Method:
For the peroxide measurement, the Reflectoquant is set-up to use
method 643 for the analysis. At a given time period after sample
dissolution, the peroxide test strip is dipped directly into a
stirred solution containing peroxide and held there for 2 seconds
and then removed and shaken to get rid of excess solution. At the
same time the test strip is placed in the solution, the 15 second
timer on the Reflectoquant Meter is activated. After removing the
excess solution from the test strip, it is inserted into the
machine and at the end of the 15 second timer, the reflectoquant
analyzes the test strip and displays the concentration of peroxide
(ppm).
Diaper Extraction Test
Representative diaper is prepared for extraction by carefully
cutting the diaper into small pieces (approximately 2-4 square
inches) over a tray to catch any materials lost from core. The
diaper material is placed in a 16 oz high density wide mouth jar
(available from VWR International; Catalog #15900-106) and treated
with 200 mL of 40:20:40 by weight mix of Denatured Ethanol (95%):
Glacial Acetic Acid: Dionized Water extraction solvent. The lid
(equipped with Plastisol liner; available from VWR International;
Catalog #16198-905) is placed tightly on the jar to ensure no
solution is lost and the jar is placed on a US Stoneware roller
type jar mill (available from VWR international; Catalog
#48900-000) on a setting of 10 for 30 minutes. The jars are placed
inside a disposable nitrile glove (such as those available from VWR
International; Catalog #40101-348) to help maintain proper contact
with the rollers of the mill and ensure proper mixing. The
extraction solvent is collected by squeezing the diaper material
within the jar and pouring the resulting liquid into a collection
container. The extraction solvent is placed in a refrigerator until
analysis and should be conducted within 3 days.
Gas Chromatography/Mass Spectrometry (GC/MS) Headspace Test
GC/MS Headspace testing is conducted using an Agilent 6890 Gas
Chromatograph equipped with a BP 5973 Mass Spectrometer and
Programmed Temperature Vaporization (PTV) injector, (Agilent, Santa
Clara, Calif.) and a Gerstel ODP Sniffport (Linthicum, Md.). The
column oven and PTV injector are plumbed for liquid nitrogen
cooling. An Agilent DB-5-MS, 60 m.times.0.32 mm i.d. column with a
1 .mu.m film thickness is used for the separation with the column
effluent split 50:50 to the sniffport and MS. A standard PTV liner
containing 25 mg of Tenax TA absorbent packed between 2 plugs of
silanized glass wool is used for injection. The auxiliary flow of
the GC is plumbed to connect to the 1/16'' fitting of the
desorption tube, and the auxiliary heater is configured to power a
syringe heater which is used to heat the desorption tube once its
needle is placed into the PTV injector. Temperatures for the MS are
set to 280.degree. C. for the transfer line, 150.degree. C. for the
quadrupole, and 230.degree. C. for the source. The MS is configured
for EI scan mode, scanning from 45-350 m/z.
Volatiles are collected on a GLT Silco.TM. coated stainless steel
desorption tube (Scientific Instruments Services, Ringoes, N.J.)
100 mm.times.4 mm i.d. containing 125 mg of Tenax TA absorbent
packed between 2 plugs of silanized glass wool. The desorption tube
is sealed with a 1/16'' female fitting at one end and a 35 mm
syringe needle at the other. As illustrated in FIG. 4, a glass 1.5
liter headspace vessel 100 consist of a top 101 which forms a
leak-free seal to the bottom 102 using an o-ring and ring clamp
103. The bottom has an inlet port 104 where the helium purge is
connected. The top 101 has an outlet port 105 with a fitting for
syringe needle of the desorption tube.
Fresh male urine is collected into sterile specimen cups (VWR
International) from about 10 subjects using the first urination of
the day and pooled together to provide a representative urine
sample. The sample absorbent article is loaded with 200 mL of the
male pooled urine at the acquisition point of the article and
placed into the headspace vessel which is sealed and allowed to age
at room temperature for 16 hours. After aging, a preconditioned,
packed, desorption tube is attached to the outlet of the headspace
vessel via the syringe needle and the inlet is attached to a
regulated helium supply. The flow is preset to deliver a 40 mL/min.
flow of helium which sweeps through the vessel and desorption tube
(which traps the volatiles swept from the vessel) for 30 minutes
yielding a 1.2 liter gas sampling of the headspace.
After collection, the desorption tube is removed from the headspace
vessel, and the needle inserted into the PTV injector. The syringe
heater is placed around the desorption tube and the auxiliary
helium flow connected. The initial temperature of the syringe
heater and PTV is 30.degree. C.; the oven temperature is 50.degree.
C.; and the auxiliary helium pressure is 8 psi. The syringe heater
is ballistically heated to a final temperature of 300.degree. C.
for a total of 20 minutes. The desorption tube is removed and the
PTV is programmed for a splitless injection: 20 psi helium flow,
purge flow 7.0 mL/min., purge time 5.0 minutes, total flow of 12.4
ml/min, and ballistically heated from 30 to 300.degree. C. starting
at 0.1 minutes.
GC oven temperature programming is held at 50.degree. C. for 2
minutes, then heated at a rate of 6.0.degree. C./min to 285.degree.
C. and held at that temperature for 10 minutes. Total Ion
Chromatograms (TIC) for the mass range of 45-350 m/z is collected
after an initial 2 minute solvent delay. Concurrently, olfactory
sniffport evaluation is conducted by the operator recording the
presence, intensity and description of the odors perceived for each
sample tested. The integrated peak area of the response of odor
specific components (for example dimethyl disulfide and
4-heptanone) is obtained from the total ion chromatogram and is
used in determining the percent reduction of the odor specific
components as compared to a control diaper with no odor control
material present (blank).
EXAMPLES
The following examples are given solely for the purposes of
illustration and are not to be construed as limitations of the
present disclosure.
Example 1
Process for Making a Bleach Activator Co-Particle
This process is practiced in a food processor (mixer), with a
vertical axis-driven impeller having a radial sweep of 8.0 cm. To a
14-speed Osterizer blender is added Sodium Nonanoyloxybenzene
sulfonate extrudate (NOBS, Future Fuels Chemical Company) which is
ground to a fine powder. In a batch wise process, 200.0 g Sodium
Percarbonate (OCI Chemical Corp, Decatur, Ala. under the tradename
Provox C) and 10.0 g ground NOBS are combined and blended together
in an Osterizer blender for 30 seconds. Next, the Sodium
Percarbonate/NOBS mixture (205.0 g) is vigorously mixed with 205.0
g of molten PEG 4600 in a preheated beaker (80.degree. C.) for
about 30 seconds. The viscous molten material is then poured onto a
strip of aluminum foil (or may alternatively be poured into a
plastic Ziploc bag) and, using spatula, spread out into a thin
layer. The ends of the aluminum foil are folded over (or the Ziploc
bag is closed) to seal the material inside and the packet is placed
into a freezer for about 15 minutes until completely solid. The
packet is removed from freezer, allowed to equilibrate to room
temperature while remaining sealed, and then the material is
removed and broken into small pieces prior to being placed back in
the Osterizer blender and ground. This procedure is carried out for
16 batches which are combined prior to sieving. The collected
material is sieved through an 850 .mu.m mesh screen and onto a 250
.mu.m. Anything collected on the 850 .mu.m mesh screen is reground
and sieved again. This process produces 3400 g of material through
850 .mu.m mesh screen and onto a 250 .mu.m mesh screen (target);
2175 g of material through a 250 .mu.m mesh screen (fines); and 624
g of material left on a 850 .mu.m mesh screen (overs).
Example 2
Process for Making a Bleach Activator Particle
This process is practiced in a Bella XL-32 paddle mixer (Dynamic
Air, St. Paul Minn.). This example describes a process to making a
bleach activator particle with a 10% loading level of bleach
activator, such as Nonanoyloxybenzene sulfonate. Twenty-four
kilograms of the core anhydrous sodium sulfate material
(Mallinckrodt Baker, Product 8024, 10-60 Mesh) is loaded into the
mixer. The mixer is started, using a paddle tip speed of 2.1 m/s.
At an elapsed time of 10 seconds, 1.2 kg of binder (Acusol 445N,
Rolm and Haas, diluted with water to a solids concentration of
about 36%) is begun to be added to the mixer, continuing at a rate
of 400 g/minute via top-spray atomization on the center fluidized
zone. At an elapsed time of 30 seconds, 3.0 kg of bleach activator
powder (Nonanoyloxybenzene sulfonate powder, Future Fuels Chemical
Company) is begun to be added to the mixer at a rate of 1.5
kg/minute. At an elapsed time of 78 seconds, 1.80 kg of micronized
anhydrous magnesium sulfate powder is begun to be added to the
mixer at a rate of 1.0 kg/minute. Mixing is continued until a total
elapsed time of 420 s, at which time the mixer is stopped and the
batch discharged. The resulting batch is sieved through 1150 um and
onto 250 um to provide 27.8 kg of bleach activator particles. To
determine the loading level of bleach activator on the core
particle, dissolve 0.100 g of the bleach activator particle in 200
mL of 40:20:40 by weight mix of Denatured Ethanol (95%): Glacial
Acetic Acid: Deionized Water and conduct the Liquid Chromatography
(LC) Test for Bleach Activator Loading Level to determine the
concentration and weight of bleach activator dissolved in the
solution. The loading level of bleach activator on the core
particle is determined by dividing the weight of bleach activator
in solution by the total weight of particle dissolved in the test
solution, and multiplying by 100. The loading level of
Nonanoyloxybenzene sulfonate bleach activator on this particle is
found to be 10.2%.
Example 3
Process for Making a Multiple Particle Bleach Activator System
To 20.0 grams of Sodium Percarbonate (ECOX-C, Kemira Kemi AB) is
added 10.0 grams of bleach activator particle as described in
Example 2 and the material is gently mixed. To determine the
relative mole ratio of peroxide:bleach activator in the multiple
particle bleach activator system, the weight and number of moles of
peroxide and bleach activator in a given weight of sample needs to
be determined. For peroxide, 0.300 g of the multiple particle
bleach activator system is dissolved in 4 L of distilled water and
after 30 minutes, the concentration of peroxide is determined using
the Reflectoquant Peroxide Test. The analysis is performed in
triplicate and the average peroxide concentration determined
(Measured--15.53 mg/L; Theoretical--15.43). The weight of peroxide
in the solution is determined by multiplying the average peroxide
concentration by the volume of water (4 L) the bleach activator
system is dissolved in. For analysis of the bleach activator, 0.300
g of the multiple particle bleach activator system is dissolved in
200 mL of 40:20:40 by weight mix of Denatured Ethanol (95%):
Glacial Acetic Acid: Deionized Water and the concentration of
Nonanoyloxybenzene sulfonate (NOBS) determined using the Liquid
Chromotagraphy (LC) Test for Bleach Activator Loading Level. The
analysis is performed in triplicate and the average NOBS
concentration determined (Measured--51.01 ppm; Theoretical--50
ppm). The weight of nonanoyloxybenzene sulfonate (NOBS) is
determined by multiplying the average NOBS concentration by the
volume of solvent (0.2 L) the bleach activator system is dissolved
in. The mole ratio of the hydrogen peroxide (delivered from the
peroxygen source) to the bleach activator is 59.3:1.
Example 4
Absorbent Article Comprising Bleach Activator System
The multiple particle bleach activator system from Example 3 is
incorporated into an unscented European Size 4 Baby Dry diaper,
distributed by The Procter & Gamble Company, Cincinnati, Ohio.
The diaper weighs from about 33.5 g to about 35 g. Said material is
incorporated by first opening up the front end seam of the diaper
by freezing the area with cold spray and carefully pulling the
topsheet away from the backsheet to fracture the glue bond. To the
opened end seam of the diaper, 0.300 g of powder from Example 5 is
added directly into the core such that the material is intermixed
with absorbent gelling material and air felt (i.e., cellulosic
fibers). The end seam is re-secured by placing 0.006 gsi glue sheet
(Bostik 2031) between the topsheet and backsheet, followed by
treatment with a roller. The closed diaper is gently shaken once to
more evenly distribute the odor control powder within the core.
The amount of bleach activator present in the diaper can be
determine by conducting the diaper extraction test followed by
performing the Liquid Chromatography (LC) Test for Bleach Activator
Loading Level analysis on the extracted liquid. The amount of
Nonanoyloxybenzene sulfonate (NOBS) determined to be in the diaper
is 10.3 mg.
Example 5
Comparative Example
Sodium percarbonate is incorporated into an unscented European Size
4 Baby Dry diaper, distributed by The Procter & Gamble Company,
Cincinnati, Ohio. The diaper weighs from about 33.5 g to about 35
g. Said material is incorporated by first opening up the front end
seam of the diaper by freezing the area with cold spray and
carefully pulling the topsheet away from the backsheet to fracture
the glue bond. To the opened end seam of the diaper, 0.200 g of
sodium percarbonate (ECOX-C, Kemira Kemi AB) is added directly into
the core such that the material is intermixed with absorbent
gelling material and air felt (i.e., cellulosic fibers). The end
seam is re-secured by placing 0.006 gsi glue sheet (Bostik 2031)
between the topsheet and backsheet, followed by treatment with a
roller. The closed diaper is gently shaken once to more evenly
distribute the odor control powder within the core.
The dimensions and values disclosed herein are not to be understood
as being strictly limited to the exact numerical values recited.
Instead, unless otherwise specified, each such dimension is
intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm".
All documents cited in the Detailed Description of the Invention
are, in relevant part, incorporated herein by reference; the
citation of any document is not to be construed as an admission
that it is prior art with respect to the present invention. To the
extent that any meaning or definition of a term in this document
conflicts with any meaning or definition of the same term in a
document incorporated by reference, the meaning or definition
assigned to that term in this document shall govern.
While particular embodiments of the present invention have been
illustrated and described, it would be apparent to those skilled in
the art that various other changes and modifications can be made
without departing from the spirit and scope of the invention. It is
therefore intended to cover in the appended claims all such changes
and modifications that are within the scope of this invention.
* * * * *